US20080125539A1 - Humidity-Hardening Binding Agent - Google Patents

Humidity-Hardening Binding Agent Download PDF

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US20080125539A1
US20080125539A1 US11/666,597 US66659705A US2008125539A1 US 20080125539 A1 US20080125539 A1 US 20080125539A1 US 66659705 A US66659705 A US 66659705A US 2008125539 A1 US2008125539 A1 US 2008125539A1
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cyclic alkyl
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Helmut Mack
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Construction Research and Technology GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to a moisture-curing binder based on polyurethane, in particular for industrial and building applications.
  • the invention further relates to a kit comprising two components for producing the moisture-curing binder, a method of producing the moisture-curing binder and a moisture-cured binder produced from the moisture-curing binder.
  • Silane-terminated polyurethanes which have at least one reactive silane group (these silane groups can contain either a hydroxyl group or a hydrolysable group such as alkoxy, acetoxy, oxime, benzamide or a chlorine atom bound to silicon), preferably two or three reactive silane groups, and can be crosslinked at room temperature have been used for a long time for producing adhesives and sealants and further industrial and building products such as levelling compositions, floor coverings, paints and varnishes, potting compositions, building foams, etc. Products having a good property profile while keeping within a sensible commercial frame can be formulated therewith.
  • joints serve to accommodate movement between individual structural elements which is caused, for example, by thermal expansion or settling processes.
  • sealants for example in accordance with DIN EN ISO 11600, are used for closing the joints.
  • Silane-modified polyether urethanes having reactive silane groups and their use in adhesives and sealants are known and described in, inter alia, U.S. Pat. No. 5,554,709, U.S. Pat. No. 4,857,623, U.S. Pat. No. 5,227,434, U.S. Pat. No. 6,197,912, U.S. Pat. No. 6,498,210 and U.S. Pat. No. 4,364,955.
  • Polyether urethanes having reactive silane groups can be prepared by various methods.
  • One possibility is to react aliphatic or aromatic diisocyanates in a stoichiometric excess with polyether polyols, which are preferably made up of ethylene oxide and/or propylene oxide, to form isocyanate-containing polyurethane prepolymers which are then reacted with aminosilanes, preferably secondary aminosilanes, to give silane-modified (silane-terminated) polyurethanes.
  • polyether polyols which are preferably made up of ethylene oxide and/or propylene oxide
  • aminosilanes preferably secondary aminosilanes
  • a further possibility is to react aliphatic and aromatic diisocyanates in a substoichiometric amount with polyether polyols, which are preferably made up of ethylene oxide and/or propylene oxide, to form hydroxyl-terminated polyurethane prepolymers which can then be reacted with an isocyanatosilane to give silane-terminated polyurethanes.
  • polyether polyols which are preferably made up of ethylene oxide and/or propylene oxide
  • a further possibility is to react monools (e.g. ⁇ -allyl- ⁇ -hydroxyl polyols) with diisocyanates, preferably aliphatic diisocyanates, to form polyurethane prepolymers having unsaturated end groups.
  • the silane groups can then be introduced via a hydrosilylation reaction with hydrogen silanes such as HSiMe(OMe) 2 or HSi(OMe) 3 in the presence of noble metal catalysts, preferably platinum catalysts. This gives silane-terminated polyurethanes.
  • polyether diols or polyether mixtures with isocyanatosilanes such as gamma- and alpha-isocyanatosilanes, particularly preferably dialkoxy- and trialkoxy-functional gamma- and alpha-isocyanatosilanes.
  • a further method of preparing silane-modified polyurethanes is the “Bayer variant”.
  • EP 596360 and U.S. Pat. No. 6,599,354 describe the preparation of an acyclic urea derivative from maleic and/or fumaric esters and aminosilanes having primary amino groups by Michael addition.
  • the acyclic urea derivatives prepared in this way are reacted with isocyanate-containing polyurethane prepolymers to give silane-terminated polyurethanes.
  • WO 2004/060953 and US 2004/0122200 state that cyclic urea derivatives containing silane groups are necessary at the ends of the silane-terminated polyurethanes prepared in this way in order to obtain good thermal stability. These are obtained by treatment of the acyclic urea derivatives with heat and acid catalysts.
  • US 2004/0087752 and WO 1996/34030 describe polydiorganosiloxane urethanes which are prepared by reacting ⁇ , ⁇ -hydroxydiorganosiloxanes, diisocyanates and polyether polyols to form hydroxyl-containing polydiorganosiloxane-urethane prepolymers.
  • US 2004/0087752 describes the subsequent reaction with isocyanatosilanes to give silane-modified polydiorganosiloxane urethanes.
  • silane-modified polyurethanes and polyurethane copolymers described are able to be activated by hydrolysis even at room temperature with elimination of the corresponding leaving group (e.g. alcohol, ketoxime, acetic acid, etc.). This is followed by a condensation reaction to form an Si—O—Si network.
  • An advantage here is that the silane crosslinking does not liberate a gaseous by-product as in the case of the classical urethane crosslinking.
  • isocyanate-free products can also be formulated largely without risk. It is known that volatile isocyanate monomers are suspected of being hazardous to health.
  • elastomers can be used for producing elastomers, sealants, adhesives, elastic adhesives, rigid and flexible foams, a wide variety of coating systems (paints and varnishes), mould-making compositions (e.g. for dental applications), potting compositions (e.g. in the automobile sector) and levelling compositions (e.g. for building applications), floor coverings, etc.
  • coating systems paints and varnishes
  • mould-making compositions e.g. for dental applications
  • potting compositions e.g. in the automobile sector
  • levelling compositions e.g. for building applications
  • floor coverings etc.
  • These products can be applied in a wide variety of ways, e.g. painting, spraying, casting, pressing, etc.
  • the polyurethanes are, inter alia, characterized by their —NH—CO—O— group in the skeleton.
  • polyurethanes are susceptible to chemical degradation by oxidation, which leads firstly to yellowing and subsequently to loss of the mechanical properties.
  • Chemical degradation of polyurethanes is often accompanied by a sharp, acrid odour.
  • Polyurethane foams tend to decompose more quickly than solid polyurethane bodies since they offer a significantly larger surface area for oxidation reactions. These sometimes also take place during production when air or nitrogen is blown through to form a foam. Oxidation is the most important degradation mechanism, but polyurethanes can also be decomposed by hydrolytic reactions. Hydrolysis leads to loss of the mechanical properties of polyurethanes.
  • Tertiary amines are often additionally present in the polymer microstructure as a result of the production processes. Photochemical degradation in the presence of oxygen forms hydroperoxides which absorb both in the UV range and in the relatively short wavelength VIS range.
  • the photostability of the polyurethane depends on the components used in its production: thus, polyurethanes derived from aromatic isocyanates are particularly unstable.
  • polyurethanes are an exception among plastics in respect of microbial attack. Their high nitrogen content makes them attractive to microorganisms.
  • a moisture-curing binder which comprises:
  • This binder can cure in the presence of moisture to form a siloxane network.
  • the invention further provides a kit for producing the moisture-curing binder of the invention, with the kit comprising the above components (i) and (ii) separately from one another, preferably in each case packed in an airtight fashion.
  • the invention provides a method of producing the moisture-curing binder of the invention, which method comprises mixing the components (i) and (ii).
  • the invention further provides for the use of the above component (i) and the above component (ii) for producing one-component or two-component elastomers, sealants, adhesives, elastic adhesives, rigid and flexible foams, coating systems such as paints or varnishes, mould-making compositions, potting compositions and levelling compositions, floor coverings, etc.
  • the invention provides a moisture-cured binder which can be obtained by curing of the moisture-curing binder of the invention in a moisture-containing atmosphere.
  • the thermal stability and the light stability and thus the weathering behaviour of moisture-cured binders based on silane-modified polyurethanes can be improved when a silane-modified acrylate polymer is mixed into the moisture-curing binders.
  • the silane-modified acrylate polymer can crosslink in the presence of moisture both with the silane-modified polyurethane and with itself.
  • the binder of the invention after curing has comparably good or improved physical properties compared to conventional binders based on silane-modified polyurethanes alone.
  • a further advantage of the invention is that the components (i) and (ii) are highly compatible with one another and form stable compositions over a wide mixing range.
  • the sealants and adhesives formulated with the binder produced in this way are well suited to the adhesive bonding and sealing of glass. Without fillers and colour-imparting materials, clear and colourless formulations can be produced. These are suitable for applications in which the adhesive join, seal or potting interface at the boundary between two substrates is to be made visually inconspicuous.
  • the moisture-curing binder of the invention is simple to produce, crosslinks rapidly, has very good storage stability, is resistant to ultraviolet light and weather influences, adheres very well to a wide variety of substrates, leads to low odour pollution during curing, can be formulated using little crosslinking catalyst and thus has excellent development potential for industrial and building applications.
  • silane-modified acrylate polymers it is possible to use silane-modified acrylate copolymers such as block copolymers, grafted copolymers, alternating copolymers or random copolymers into which moisture-reactive silanes such as alkoxysilanes have been copolymerized during their preparation.
  • the preparation of acrylate polymers and also the preparation of silane-modified acrylate polymers is generally known.
  • the polymerization can be carried out free-radically or ionically or by metal catalysis.
  • a mercaptan such as a mercaptosilane
  • alkyl acrylates i.e. alkyl acrylates or alkyl methacrylates
  • MMA methyl methacrylate
  • nBMA n-butyl methacrylate
  • SMA stearyl methacrylate
  • the crosslinkers are highly reactive, have low volatility and have at least two polymerizable functions in a molecule.
  • Acrylate and methacrylate polymers are preferably prepared so that desired structure-property relationships are obtained.
  • Such polymerization processes are, for example, ionic polymerization and living polymerization. These allow targeted construction of the polymer structures. They make it possible to obtain narrow molecular weight distributions, to determine the type and number of the end groups and, in the preparation of block copolymers, to set the number of blocks, the block length and the block length distribution.
  • Free-radical polymerization is the most widespread process for preparing synthetic polymers. Bulk plastics such as LDPE, PVC and PMMA in particular are produced virtually exclusively by free-radical polymerization. Free-radical polymerization is a chain reaction. Chain initiation, chain growth and chain termination occur in parallel. Initiators used are compounds which, as a result of the introduction of energy, form free radicals, e.g. azo or peroxy compounds. These free radicals react with the monomers and initiate the chains. During chain growth, the free radicals formed at the initiation of the chain add on further monomers in a multiple addition and thus form the polymer chains. The free radicals are highly reactive and react with one another in combination or disproportionation reactions at a diffusion-controlled rate.
  • a further possible reaction is transfer of the active site to, for example, another chain, a monomer, a solvent molecule or a specifically added chain transfer agent, e.g. a mercapto compound such as DS MTMO, DS MTEO, etc.
  • Living polymerization is defined as a chain reaction without irreversible transfer and termination reactions which leads to defined polymers.
  • concentration of the active species and the number of polymer chains remain constant during the course of the polymerization. In the ideal case, the molecular weight distribution corresponds to a Poisson distribution.
  • a living polymerization which meets these prerequisites can be carried out anionically and with restrictions cationically or by means of group transfer. Living polymerization requires an increased outlay for the preparation. Since in the living polymerization the chain ends remain active even after complete conversion, block copolymers can be obtained by sequential addition of various monomers and end-functionalized polymers can be obtained by targeted addition of termination reagents. The combination of these processes makes it possible to build up many complicated polymer architectures, e.g. star copolymers, comb copolymers and graft copolymers and also diblock, triblock or multiblock copolymers.
  • Controlled radical polymerization was developed in the middle of the 1990s and combines the advantages of free-radical polymerization such as large selection of monomers and ease of implementation (e.g. insensitivity toward water and impurities) with the advantages of living ionic polymerization, e.g. narrow molecular weight distributions, formation of complex polymer architectures and introduction of defined end groups.
  • controlled radical polymerization is based on an active species and a dormant species. Only the active species is polymerization-active, but the two species are in an equilibrium which is far to the side of the dormant, inactive species. Exchange between the species occurs quickly and reversibly. The consequence is a very low steady-state concentration of free radicals. The termination reactions are suppressed relative to the growth reactions. The number of terminated chains is therefore negligibly small.
  • This controlled (or “living”) radical polymerization thus allows, like living ionic polymerization, control of the course of the polymerization and thus the polymer architecture.
  • the molecular weight distribution therefore corresponds to a Poisson distribution in the ideal case.
  • ATRP atom transfer radical polymerization (the most important catalyst system is Cu(I)Cl/bipyridine)
  • SFRP stable free-radical polymerization
  • RAFT reversible addition fragmentation chain transfer process.
  • ATRP in particular allows the use of many monomers, e.g. also acrylates and methacrylates.
  • monomers e.g. also acrylates and methacrylates.
  • the wide range of initiator/catalyst systems makes ATRP very flexible in terms of the choice of reaction conditions, e.g. temperature and solvent.
  • the removal of the copper salts is a cost problem. Colour problems can occur in the use of the products.
  • redox processes can occur between the copper salts and the iron. This is countered by immobilization of the catalyst (e.g. on silica gel, polystyrene, etc.).
  • solvents such as supercritical carbon dioxide or ionic liquids are further proposals.
  • Telechelic polymers are polymers and/or oligomers which have a low molecular weight (M n from about 1000 to 12 000) and two defined, reactive end groups. They make it possible to prepare defined structures such as block copolymers or networks for applications in the surface coatings, adhesives and sealants industry. Telechelic polymers can be prepared by use of suitable initiators, termination reagents or transfer reagents or by chain-analogous reaction. The best-known reactions for preparing telechelic polymers which have a functionality of precisely two are polyaddition (e.g. polyurethanes, polyureas), polycondensation (e.g. polyamide, polycarbonate, polyester) and ring-opening polymerization of heterocyclic monomers (e.g. cyclic esters, carbonates, ethers), if appropriate using termination reagents which contain the desired groups.
  • polyaddition e.g. polyurethanes, polyureas
  • polycondensation e.g.
  • “dead-end” polymerization is used for preparing telechelic polymers.
  • a large excess of an initiator which bears the desired functional group is used for this purpose (e.g. telechelic polymers containing carboxyl or hydroxyl groups).
  • the polymerization can be carried out in the presence of a suitable chain transfer reagent (e.g.
  • telomerization a process for converting a silane into a silane into a silane.
  • a first step chains are initiated by means of catalytic amounts of peroxo or azo initiators.
  • the growing chains react randomly with the chain transfer agent with, for example, halogen abstraction and the resulting free radical is again able to start a new chain. This process is referred to as “telomerization”.
  • Telechelic polymers can also be prepared by living ionic polymerization or by means of ATRP.
  • the ATRP which can be employed for preparation of telechelic polymers is based on the reversible exchange of a halogen atom between initiator or growing polymer chain and a catalyst system containing a transition metal (e.g. Cu, Fe, Co, Ru, etc.). This enables free radical concentrations to be kept low and the typical termination reactions of free-radical polymerization thus to be suppressed.
  • Telechelic polymers based on acrylates and methacrylates and having a narrower molecular weight distribution than is possible by means of classical polymerization methods can be prepared by means of ATRP. It is possible to use bifunctional initiators.
  • halogen-terminated telechelic polymer is formed by monodirectional or bidirectional growth.
  • a large number of functional groups, e.g. alkoxysilane end groups, can be produced from the halogen end groups by chain-analogous reaction.
  • Silane-modified acrylate polymers which can be used for the present invention are described, for example, in U.S. Pat. No. 4,333,867 and U.S. Pat. No. 1,096,898.
  • silane-modified acrylate polymers for the present invention monomers containing silane groups (preferably alkoxysilane groups), e.g. vinylsilanes, acrylsilanes or methacrylsilanes, can be copolymerized with the acrylate monomers by one of the abovementioned processes.
  • the silane-modified acrylate polymer for use in the binders of the invention is obtainable by copolymerization of a silane of the formula (I):
  • the silane-modified acrylate polymer obtained then preferably contains silane groups having one of the following formulae:
  • the substituted or unsubstituted, linear or cyclic alkyl group as the radical R can contain from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms.
  • Linear and cyclic alkyl groups, which may be substituted, are preferred for R.
  • substituents of the linear or cyclic alkyl group are alkyl and alkoxy groups having from 1 to 6 carbon atoms. Multiple substitution is possible.
  • the linear or cyclic alkyl groups are preferably unsubstituted or monosubstituted. Examples of linear alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl. Examples of cyclic alkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the aryl group as the radical R can be, for example, phenyl or naphthyl.
  • the aralkyl group is preferably an Ar-C 1-6 -alkyl group. Possible substituents of the aryl or aralkyl group correspond to those for the linear or cyclic alkyl groups, and these substituents can also substitute the aryl group.
  • the alkoxy group and the acyloxy group can contain from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms. Possible substituents on the alkoxy group and the acyloxy group correspond to those for the linear or cyclic alkyl groups.
  • the substituted or unsubstituted, linear or cyclic alkyl group and the substituted or unsubstituted aryl or aralkyl group as R 2 and R 3 generally correspond to those indicated for the radical R, except that the number of carbon atoms of the substituted or unsubstituted, linear or cyclic alkyl group can be from 1 to 20.
  • Particularly preferred radicals R 2 are methyl and n-butyl.
  • R 3 is particularly preferably methyl.
  • silanes of the formula (I) are MEMO (3-methacryloxypropyltri-methoxysilane), methyl-MEMO (methacryloxypropylmethyldimethoxysilane), ACMO (acryloxy-propyltrimethoxysilane), VTEO (vinyltriethoxysilane), VTMOEO (vinyltris(2-methoxy-ethoxy)silane).
  • MEMO 3-methacryloxypropyltri-methoxysilane
  • methyl-MEMO methacryloxypropylmethyldimethoxysilane
  • ACMO acryloxy-propyltrimethoxysilane
  • VTEO vinyltriethoxysilane
  • VTMOEO vinyltris(2-methoxy-ethoxy)silane.
  • a plurality of different silanes of the formula (I) can be used for the copolymerization.
  • the substituted or unsubstituted, linear or cyclic alkyl group or substituted or unsubstituted aryl or aralkyl group R 4 , R 5 , R 6 and R 7 independently correspond to those indicated above for R 2 and R 3 .
  • the alkenyl groups, acyloxy groups and alkoxycarbonyl groups R 4 , R 5 , R 6 and R 7 are independent of one another and can have from 1 to 10, preferably from 1 to 6, carbon atoms.
  • Halogen as R 4 , R 5 , R 6 and R 7 can be, in each case independently, fluorine, chlorine, bromine or iodine, with chlorine and fluorine being preferred.
  • R 4 is particularly preferably hydrogen or methyl, i.e. the compound of the formula (II) is preferably a (meth)acrylate.
  • R 5 is particularly preferably methyl, ethyl, propyl, n-butyl, i-butyl, decyl, dodecyl, cyclohexyl, stearyl, benzyl, 2-hydroxyethyl and 2-ethylhexyl.
  • acrylates of the formula (II) are acrylic acid, methacrylic acid, acrylonitrile, methyl acrylate, ethyl acrylate, n/iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, glycidyl acrylate, stearyl acrylate, methyl methacrylate, n/iso-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, stearyl methacrylate, glycidyl methacrylate, acrylamide. These and other acrylates can be selected according to the desired properties of the silane-modified acrylate polymer to be obtained and can be combined with one another.
  • olefins of the formula (III) are ethylene, propylene, isoprene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, chlorostyrene, pyridine, 2-methylstyrene, divinylbenzene. These and other olefins can be selected according to the desired properties of the silane-modified acrylate polymer to be obtained and can be combined with one another.
  • silanes of the formula (I) can be used in the monomer mixture and subjected to the copolymerization.
  • the acrylate of the formula (II) and the olefin of the formula (III) together preferably make up at least 60% by weight, particularly preferably at least 80% by weight and most preferably at least 90% by weight, of the mixture for the copolymerization.
  • the proportion of the acrylate of the formula (II) is at least 50% by weight, preferably at least 75% by weight and most preferably at least 85% by weight, based on the total amount of monomers of the formula (II) and monomers of the formula (III).
  • regulators for the copolymerization for example amines (e.g. triethylamine, tripropylamine or tributylamine), halogen compounds (e.g. chloroform, carbon tetrachloride or carbon tetrabromide), mercaptans (e.g. 1-butanethiol, 1-hexanethiol, 1-dodecanethiol, ethyl disulphide, phenyl disulphide or butyl disulphide), alcohols (e.g.
  • ethanol n-/iso-propanol or n-/iso-/tert-butanol
  • mercaptosilanes or sulphur silanes e.g. Si 69, preferably MTMO, MTEO (3-mercaptopropyltriethoxysilane) or methyl-MTMO.
  • Si 69 preferably MTMO, MTEO (3-mercaptopropyltriethoxysilane) or methyl-MTMO.
  • MTMO MTMO
  • MTEO 3-mercaptopropyltriethoxysilane
  • methyl-MTMO methyl-MTMO
  • peroxo compounds e.g. benzoyl peroxide, benzoyl hydroperoxide, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, acetyl peroxide, lauryl peroxide, hydrogen peroxide, persulphuric acid or diisopropyl peroxydicarbonate
  • azo compounds e.g. AIBN or substituted AIBN
  • the polymerization can be carried out in inert solvents such as diethyl ether, methyl ethyl ether, methyl cellosolve, pentane, hexane, heptane, xylene, benzene, toluene, methyl acetate, ethyl acetate, butyl acetate, etc.
  • the polymerization temperature depends on the initiator used and is preferably in the range from 45° C. to 180° C.
  • the monomer mixture can be added a little at a time or continuously. This allows the evolution of heat to be controlled.
  • the unsaturated silanes such as ⁇ - and ⁇ -MEMO, methyl-MEMO, etc., are incorporated into the acrylate/methacrylate copolymer skeleton and in the presence of moisture act as crosslinking points.
  • the mechanical properties can be controlled via, for example, the monomer mixture, the amount of silane and the other reaction parameters (e.g. amount of regulator).
  • Silane-modified polyurethanes suitable for use in the present invention and methods of preparing them are known in the prior art (see introduction).
  • Preferred polyurethanes are ones based on polyalkylene glycol ethers (polyoxyalkylenes) or diorganosiloxanes (preferably dimethylsiloxane) as diol component.
  • Such polyurethanes can be prepared as prepolymers and subsequently be silane-modified.
  • the silane modification generally takes place at the ends of the linear polyurethanes, so that the silane-modified polyurethanes for use in the present invention are preferably silane-terminated polyurethanes.
  • a number of silane-modified polyurethanes and their preparation are described below.
  • NCO-terminated polyurethane prepolymers are prepared in a first step by using the isocyanate in excess.
  • the polyurethane prepolymer can be prepared from OH-terminated linear or branched diols or triols (preferably linear diols) with aliphatic or aromatic polyisocyanates (preferably diisocyanates).
  • the polyurethane prepolymer can also be prepared from aliphatic alcohols or OH-terminated linear and/or branched diols or triols with a mixture of aliphatic and/or aromatic monoisocyanates or diisocyanates. This reaction is carried out in the temperature range from 30° C. to 120° C., preferably from 40° C. to 100° C., particularly preferably from 40° C. to 80° C.
  • NCO/OH equivalence ratio of from 1.1:1 to 3:1, preferably from 1.2:1 to 1.7:1, particularly preferably from 1.3:1 to 1.6:1, can be employed in the reaction.
  • the amine or organometallic catalysts known from polyurethane chemistry e.g. as described in U.S. Pat. No. 5,554,709, U.S. Pat. No. 4,857,623 and U.S. Pat. No. 6,498,210
  • polyurethane chemistry e.g. as described in U.S. Pat. No. 5,554,709, U.S. Pat. No. 4,857,623 and U.S. Pat. No. 6,498,210
  • the silane-modified polyurethane can be obtained from the resulting polyurethane prepolymer having isocyanate end groups by reaction with a silane of the formula (IV):
  • the group Y can react with a terminal —NCO group, making it possible to obtain, for example, polyurethanes which contain end groups of one of the following formulae:
  • R 12 is particularly preferably methyl.
  • R 13 is particularly preferably methyl, ethyl, n-propyl, i-propyl or n-butyl.
  • R 14 is most preferably methyl or n-butyl.
  • R 14 is then preferably a substituted or unsubstituted, linear or cyclic alkyl group having from 1 to 20 (preferably from 1 to 10, more preferably from 1 to 6) carbon atoms, a substituted or unsubstituted phenyl or phenylalkyl group or -A-SiR′(OR 11 ) p (OR 13 ) q .
  • the phenylalkyl group can be a phenyl-C 1-6 -alkyl group, preferably a phenyl-C 1-3 -alkyl group such as benzyl.
  • R 14 is -A-SiR′(OR 11 ) p (OR 13 ) q
  • Y is preferably —NHR 14 .
  • the radicals defined therein can be identical or different.
  • Preferred classes of compounds of the formula (IV) in which R 14 is -A-SiR′(OR 11 ) p (OR 13 ) q are those in which A is a linear alkylene group having from 1 to 6, particularly preferably from 1 to 3, carbon atoms, e.g. the classes of the formulae HN[—CH 2 —CH 2 —CH 2 — SiR′(OR 11 ) p (OR 13 ) q )] 2 and HN[—CH 2 —SiR′(OR 11 ) p (OR 13 ) q )] 2 .
  • Examples of such compounds are ⁇ - and ⁇ -bis-AMMO (AMMO is 3-aminopropyltrimethoxysilane) and bis-AMEO (AMEO is 3-aminopropyltriethoxysilane).
  • the silane-modified polyurethane is preferably a metal-free silane-modified polyurethane, i.e. the above-described silane modification is preferably carried out in the absence of a metal catalyst in order to avoid traces of metal in the product.
  • metal-free silane-modified polyurethanes are comprehensively described in EP 1 245 602. The contents of EP 1 245 602 are hereby incorporated by reference.
  • the silane-modified polyurethane should have a molecular weight of from 250 to 60 000, preferably from 300 to 40 000, particularly preferably from 1000 to 30 000.
  • polyether diols prepared, for example, in the KOH process and having a molecular weight of from 1500 to 2000 can be used for the preparation of the NCO-terminated polyurethane prepolymers.
  • such prepolymers have relatively high viscosities.
  • the formulation is associated with handling difficulties and should, for example, be compensated for by addition of plasticizer and a relatively low filler content.
  • Another method is the use of high molecular weight polyether diols (Acclaim®) which have a low degree of unsaturation and are prepared, for example, by the metal cyanide process (see U.S. Pat. No. 5,227,434, WO 2004/060953 and DE 19849817).
  • Acclaim® high molecular weight polyether diols
  • Preference is given to using polyols based on propylene oxide and having molecular weights of from 100 to 20 000, preferably from 500 to 15 000, particularly preferably from 1000 to 12 000.
  • Suitable polyols are, for example, polyoxyalkylene diols (in particular polyoxyethylene, polyoxypropylene and polyoxybutylene), polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols and comparable compounds.
  • Further polyols which can be used are, for example, tetraols, pentaols, hexaols, alkoxylated bisphenols or polyphenols, sugars and sugar derivatives (e.g. sorbitol, mannitol, pentaerythritol) and also Poly bd® polymers.
  • a polyurethane molecule can contain two or more different diol components. It is also possible to use mixtures of different types of polyurethanes which are based on different diol components.
  • isocyanate for preparing the polyurethane prepolymers it is possible to use aliphatic, cycloaliphatic and/or aromatic diisocyanates of the prior art which preferably have an isocyanate content of from 20 to 60% by weight.
  • OH-terminated polyurethane prepolymers are prepared in a first step by using the isocyanate in a substoichiometric amount.
  • the polyurethane prepolymers can be prepared from OH-terminated linear and/or branched diols and/or triols (preferably linear diols) and aliphatic and/or aromatic diisocyanates.
  • the polyurethane prepolymers can also be prepared from aliphatic alcohols such as OH-terminated linear and/or branched diols and/or triols and a mixture of aliphatic and/or aromatic monoisocyanates and diisocyanates.
  • the reaction can be carried out in the temperature range from 30° C.
  • amine or organometallic catalysts known per se from polyurethane chemistry can be used in the preparation.
  • the resulting OH-terminated polyurethane prepolymer is then silane-modified by means of an isocyanatosilane of the formula (V):
  • silane-modified polyurethanes which have end groups of the following formula:
  • the silane-terminated polyurethane should have a molecular weight of from 250 to 60 000, preferably from 300 to 40 000, particularly preferably from 1000 to 30 000.
  • polyether diols prepared, for example, in the KOH process and having a molecular weight of from 1500 to 2000 can be used for the preparation of the NCO-terminated polyurethane prepolymers.
  • such prepolymers have relatively high viscosities.
  • the formulation is associated with handling difficulties and should, for example, be compensated for by addition of plasticizer and a relatively low filler content.
  • Another method is the use of high molecular weight polyether diols (Acclaim®) which have a low degree of unsaturation and are prepared, for example, by the metal cyanide process (see U.S. Pat. No. 5,227,434, WO 2004/060953 and DE 19849817).
  • Acclaim® high molecular weight polyether diols
  • Preference is given to using polyols based on propylene oxide and having molecular weights of from 100 to 20 000, preferably from 500 to 15 000, particularly preferably from 1000 to 12 000.
  • Suitable polyols are, for example, polyoxyalkylene diols (in particular polyoxyethylene, polyoxypropylene and polyoxybutylene), polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols and comparable compounds.
  • Further polyols which can be used are, for example, tetraols, pentaols, hexaols, alkoxylated bisphenols or polyphenols, sugars and sugar derivatives (e.g. sorbitol, mannitol, pentaerythritol) and also Poly bd® polymers.
  • isocyanate used for preparing the polyurethane prepolymers it is possible to use those which have been mentioned above for process a).
  • ⁇ -silanes e.g. OCN—CH 2 —Si(OR) 3
  • ⁇ -silanes e.g. OCN—CH 2 —CH 2 —CH 2 —Si(OR) 3
  • the increased reactivity of the alpha-silanes also results in a decreased storage stability (dimer or trimer formation) of the silane and of the silane-modified or silane-terminated polyurethane prepared in this way.
  • the preparation of the polyurethane prepolymer having terminal isocyanate groups can be carried out as in process a). Subsequent reaction of the NCO-terminated prepolymers prepared in this way with an acyclic urea derivative, which can be prepared from maleic and/or fumaric esters and aminosilanes having primary amino groups by Michael addition, gives the silane-modified polyurethanes.
  • acyclic urea derivative which can be prepared from maleic and/or fumaric esters and aminosilanes having primary amino groups by Michael addition, gives the silane-modified polyurethanes.
  • the “BAYER variant” is described, inter alia, in EP596360 and U.S. Pat. No. 6,599,354.
  • WO 2004/060953 and US 2004/0122200 state that cyclic urea derivatives containing silane groups are necessary at the ends of the silane-terminated polyurethanes prepared in this way to achieve good thermal stability. These can be obtained by treatment
  • silane-modified polyurethanes prepared by the methods a) to c) are commercially available as, for example, Desmoseal® LS 2237 (Bayer AG), Polymer ST50 (Hanse Chemie GmbH), Permapol® MS (Courtaulds Coatings Incorporated) or WSP 725-80 (Witton Chemical Company). They complement the silane-terminated polyoxyalkylenes on offer. Suppliers of these are, for example, Kaneka Corporation (MS Polymer® S203H and S303H) and Asahi Glass (Excestar® S2410 and S2420).
  • Silicones and polyurethanes complement one another over a wide range.
  • Polyurethanes generally have very good mechanical properties while silicones retain their elasticity, in particular, at low temperatures.
  • silicones are water-repellent. The reaction of an NCO-terminated polyurethane-silicone prepolymer with aminosilanes is described below.
  • Polyurethane prepolymers having terminal isocyanate groups can be obtained by reacting an excess of an isocyanate with ⁇ , ⁇ ⁇ -OH-polydiorganosiloxanes.
  • the organic groups in the ⁇ , ⁇ -OH-polydiorganosiloxanes are preferably linear alkyl groups having from 1 to 6, preferably from 1 to 3, carbon atoms. Particular preference is given to ⁇ , ⁇ -bishydroxypolydimethyl-siloxanes. In addition, it is possible to use polyols.
  • polyurethane prepolymers can be silane-modified by means of an aminosilane or mercaptosilane, preferably a secondary ⁇ - or ⁇ -aminosilane or ⁇ - or ⁇ -mercaptosilane.
  • Polyurethane prepolymers having terminal hydroxy groups can be obtained by reacting a substoichiometric amount of an isocyanate with ⁇ , ⁇ ⁇ -OH-polydiorganosiloxanes.
  • polyols it is possible to use polyols.
  • These polyurethane prepolymers can be silane-modified by means of an isocyanatosilane, preferably a ⁇ - or ⁇ -isocyanatosilane.
  • the moisture-curing binders of the invention can be produced by simple physical mixing of a silane-modified polyurethane (i) and a silane-modified acrylate polymer (ii), e.g. on the basis of a solids content of 50% by weight of a silane-modified polyurethane (i) to 50% by weight of a silane-modified acrylate polymer (ii).
  • Mixing ratios of the silane-modified polyurethane (i) to a silane-modified acrylate polymer (ii) of from 99:1% by weight to 1:99% by weight are possible.
  • Preference is given to mixing ratios of from 10:90 to 90:10% by weight, particularly preferably from 20:80 to 90:10% by weight.
  • Mixing ratios of (i) to (ii) of from 65:35 to 90:10% by weight are most preferred.
  • plasticizers e.g. ones based on Mesamoll®, aliphatic and/or aromatic hydrocarbons, phthalates (e.g. DIUP, DIDP, DIOP, etc.), polyoxyalkylenes, carboxylic esters (e.g. adipic esters, sebacic esters, etc.), etc.
  • water scavengers e.g. silane-based water scavengers (e.g.
  • VTMO vinyltrimethoxysilane
  • VTEO vinyltriethoxysilane
  • 6490 Si(OEt) 4 , HMDS, etc.
  • oxide-based water scavengers e.g. CaO
  • isocyanate-based water scavengers Preference is given to adding from 0.1% by weight to 10% by weight of water scavengers, particularly preferably from 0.2% by weight to 1.5% by weight of water scavengers, based on the total mixture of the moisture-curing binder.
  • One-component and two-component elastomers, sealants, adhesives, elastic adhesives, rigid and flexible foams, a wide variety of coating systems (paints and varnishes), mould-making compositions (e.g. for dental applications), potting compositions (e.g. in the automobile sector) and levelling compositions (e.g. for building applications), floor coverings, etc., can be formulated using the novel binders.
  • These products can be applied in a wide variety of ways, e.g. painting, spraying, casting, pressing, etc.
  • the novel binders are preferably used for producing adhesives and sealants and also elastic adhesives.
  • Customary further constituents of a formulation of the binder of the invention are solvents, fillers, pigments, plasticizers, stabilizing additives, water scavengers, bonding agents, thixotropes, crosslinking catalysts, tackifiers, etc.
  • solvents e.g. aromatic hydrocarbons (e.g. toluene, xylene, etc.), esters (e.g. ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.), ketones (e.g. methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.), etc.
  • aromatic hydrocarbons e.g. toluene, xylene, etc.
  • esters e.g. ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.
  • ketones e.g. methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.
  • the solvent can be added during the course of the free-radical polymerization.
  • the binders of the invention can be formulated with or without fillers.
  • fillers it is possible to use both extender fillers and reinforcing fillers.
  • Extender fillers can make up more than 50% by weight of the total formulation. Preference is given to 350 parts by weight of filler per 100 parts by weight of binder, particularly preferably from 50 to 150 parts by weight of filler per 100 parts by weight of binder.
  • Extender fillers and reinforcing fillers, surface-treated and/or not surface-treated are, for example, natural and precipitated chalks (e.g.
  • kaolin calcined kaolin, clay, talc, wollastonite, etc.
  • aluminium hydroxide magnesium hydroxide, quartz, cristoballite, barium sulphate, glass spheres, zeolites, zinc oxide, nephelinic syenite, layered silicates (e.g. bentonite, clay earth, etc.), feldspar, dolomite, magnesium carbonate, metal powders (e.g. zinc, iron, aluminium, etc.) and comparable fillers.
  • a formulation using pyrogenic oxides e.g. Aerosil®
  • the pigments can be of organic or inorganic origin (e.g. titanium dioxide, including pyrogenic titanium dioxide, effect pigments based on aluminium, e.g. from Eckart or Silberline, azo dyes, etc.).
  • the proportion of pigments in the formulation is preferably from 0 to 80 parts per 100 parts by weight of binder, particularly preferably from 0 to 20 parts by weight.
  • plasticizers e.g. to exert a positive influence on the final properties of the product or to improve the compatibility of the filler with the binder (e.g. in order to achieve higher filler contents)
  • customary phthalates e.g. Jayflex®, Palatinol®, etc., dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, etc.
  • aliphatic dicarboxylic esters e.g.
  • dioctyl adipate, dioctyl sebacate, etc. polyalkylene glycol esters (e.g. Bezoflex® 50 and 400, etc., diethylene glycol dibenzoate, triethylene glycol dibenzoate, etc.), chlorinated hydrocarbons, hydrocarbon oils (e.g. alkylbiphenyl, partially hydrogenated terphenyl, etc.), Mesamoll®, Novares®, epoxidized soya oil (e.g. Flexol® EPO) or mixtures thereof.
  • the plasticizer can be added during the course of the free-radical polymerization.
  • dispersants can be used during the process of formulation (e.g. Dispex®, low-viscosity polyacrylates, etc.).
  • the proportion of plasticizer in the formulation is preferably from 5 to 150 parts by weight per 100 parts by weight of binder, particularly preferably from 30 to 100 parts by weight.
  • Stabilizing additives such as ultraviolet light stabilizers and/or antioxidants can likewise be included in the formulation. From 0 to 30 parts by weight per 100 parts by weight of binder are usual and preferred, with particular preference being given to from 0 to 10 parts by weight.
  • the stabilizing additives can be obtained, for example, from Great Lakes and Ciba Specialty Chemicals under the trade names Anox® 20 and Uvasil® 299 HM/LM or Irganox® 1010 and 1076 and Tinuvin® 327, 213 and 622 LD, etc.
  • Water scavengers/desiccants can be inorganic oxides such as CaO, etc., zeolites and/or monomeric, oligomeric and/or cooligomeric silanes, e.g. DYNASYLAN®, Silquest®, DYNASIL®, etc. Preference is given to using VTMO, MTMS, 6490 and/or DYNASIL® A.
  • the formulation of storage-stable products without water scavengers/desiccants requires predrying of the fillers and pigments. From 0 to 20 parts by weight per 100 parts by weight of binder are usual and preferred, with particular preference being given to from 0 to 10 parts by weight.
  • bonding agents it is possible to use customary monomeric and oligomeric organosilanes such as DYNASYLAN®, Geniosil®, Silquest® and DYNASIL® (Degussa AG), preferably alpha- and gamma-AMEO, -AMMO, -DAMO, -1411, -TRIAMO, -1505, etc., particularly preferably alpha- and gamma-AMMO, 1146, alpha- and gamma-GLYMO, etc., or mixtures thereof.
  • the bonding agent influences the hardness of the crosslinked product.
  • the formulation can also contain no bonding agent. It is then advisable to apply a primer to the substrate before application of the product.
  • epoxides phenolic resins, titanates, zirconates, aromatic polyisocyanates, etc.
  • bonding agents From 0 to 20 parts by weight per 100 parts by weight of binder are usual and preferred, with particular preference being given to from 0 to 5 parts by weight.
  • thixotropes As thixotropes (“antisagging” agents), it is possible to use microcrystalline polyamide waxes (e.g. Disparlon®, Crayvallac®, Thixatrol®, etc.), silicas (e.g. Aerosil®, Cab-O-Sil®, HDK®, etc.), hydrogenated castor oil (e.g. castor wax from CasChem, Thixcin® from Rheox, etc.), metal soaps (e.g. calcium stearate, aluminium stearate, barium stearate, etc.), surface-treated clays and kaolins, etc. Depending on the fillers used, the formulation can also contain no thixotrope. The proportion of thixotrope in the formulation is preferably from 0 to 50 parts by weight per 100 parts by weight, particularly preferably from 0 to 15 parts by weight.
  • Crosslinking catalysts are the customary organic tin, lead, mercury and bismuth catalysts, e.g. dibutyltin dilaurate (e.g. from BNT Chemicals GmbH), dibutyltin diacetate, dibutyltin diketonate (e.g. Metatin® 740 from Acima/Rohm+Haas), dibutyltin dimaleate, tin naphthenate, etc. It is also possible to use reaction products of organic tin compounds, e.g. dibutyltin dilaurate, with silicic esters (e.g. DYNASIL® A and 40), as crosslinking catalysts. Titanates (e.g.
  • the proportion of crosslinking catalyst in the formulation is preferably from 0.01 to 20 parts by weight per 100 parts by weight of binder, particularly preferably from 0.01 to 10 parts by weight.
  • pressure sensitive adhesives can be, for example, resin acid esters (rosin, terpentine, etc.), phenolic resins, aromatic hydrocarbon resins, xylene-phenol resins, coumarin resins, petroleum resins, low molecular weight polystyrene, 1,2-polybutadienes having a molecular weight of from about 1000 to 3000, including hydroxy-terminated 1,2-polybutadienes, Polyvest®, Polyoil® LCB 110 and LCB 130, etc.
  • Possible substrates for pressure sensitive adhesives are, for example, tapes, sheets, films, labels, etc.
  • the pressure sensitive adhesive can be applied in situ, as solution (e.g.
  • the proportion of tackifier in the formulation is preferably from 0 to 100 parts by weight per 100 parts by weight of binder, particularly preferably from 0 to 50 parts by weight.
  • the percentage of free NCO groups can be determined, for example, by titration (ASTM D 2572) or IR spectroscopy.
  • the polymers 1, 2, 3 and 4 prepared in Examples 1 to 4 are in each case intimately mixed with the silane-modified acrylate polymer (polymer 5) in a mixing ratio of 70% by weight:30% by weight and 90% by weight:10% by weight for 1 hour at 50° C. with exclusion of moisture and subsequently cooled to room temperature.
  • the compatibility is examined after storage with exclusion of moisture.
  • Polymer 3 is intimately mixed with polymer 5 in a ratio of 90% by weight:10% by weight for 1 hour at 50° C. with exclusion of moisture and subsequently cooled to room temperature.
  • vinylsilane desiccant 0.06 part by weight of crosslinking catalyst (Metatin® 740) are added.
  • the mixture is mixed at 40° C. for 1 hour at atmospheric pressure and subsequently degassed at ⁇ 5 mm of Hg for 5 minutes. It is subsequently packed in cartridges.
  • the silane-modified polymer 1 is intimately mixed with the silane-modified polymer 5 in a ratio of 80% by weight:20% by weight for 1 hour at 50° C. with exclusion of moisture and subsequently cooled to room temperature.
  • the mixture produced in this way and, separately therefrom, the silane-modified polyurethane 1 are then admixed with 1.5 parts by weight of aminosilane bonding agent (DYNASYLAN® AMMO) and 0.06 part by weight of crosslinking catalyst (Metatin® 740) and crosslinked at 23° C. and 50% relative atmospheric humidity for 14 days.
  • the crosslinked binders are stored at 80° C. in a convection drying oven for 1 week and the colour change before and after storage is determined by means of a Minolta Chromameter® CR 300.
  • Binder formulation with polymer 1 is
  • the thermal stability (here yellowing tendency) of the crosslinked binder based on polymer 1 can be improved by addition of polymer 5.
  • the tensile peeling test was carried out in accordance with ASTM C 794 (“adhesion-in-peel”).
  • the chosen substrate glass was cleaned with isopropanol, detergent and demineralized water and dried in air.
  • Binder 1 is intimately mixed with binder 5 in a ratio of 80% by weight:20% by weight for 1 hour at 50° C. with exclusion of moisture and subsequently cooled to room temperature.
  • the mixture produced in this way and, separately therefrom, polymer 1 are then admixed with 1.5 parts by weight of aminosilane bonding agent (DYNASYLAN® AMMO) and 0.06 part by weight of crosslinking catalyst (Metatin® 740).
  • the formulated binders produced in this way are applied in a thickness of about 1.5 mm to glass by doctor blade and subsequently covered with an aluminium shield (hole size: about 120 ⁇ m). Another about 1.5 mm of sealant (binder) are applied to the aluminium shield by doctor blade.
  • the test specimens produced in this way are crosslinked at 23° C. and 50% relative atmospheric humidity for 14 days.
  • the crosslinked test specimens are exposed to ultraviolet light for 350 hours in a QUV oven.
  • the glass side faces the ultraviolet light source.
  • the QUV test was carried out in a cycle of 4 h/60° C./high atmospheric humidity/light on and 4 h/20° C./high atmospheric humidity/light off.
  • the adhesion after ultraviolet light ageing of the crosslinked binder with polymer 1 can be improved by addition of polymer 5.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyurethanes Or Polyureas (AREA)
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EP1812525A1 (fr) 2007-08-01
JP2008520777A (ja) 2008-06-19
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DE102004055450A1 (de) 2006-05-18

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